EP1883686A2

EP1883686A2 - Pressure-sensitive adhesive mass and method for the production thereof

Info

Publication number: EP1883686A2
Application number: EP06754969A
Authority: EP
Inventors: Thilo Dollase; Aranzazu Escudero Vallejo; Bernd Lühmann
Original assignee: Tesa SE
Current assignee: Tesa SE
Priority date: 2005-05-12
Filing date: 2006-05-03
Publication date: 2008-02-06
Also published as: US8372932B2; EP3235888A2; JP2008540750A; DE102005022782A1; US20060257650A1; US20110039970A1; WO2006120136A2; WO2006120136A3; EP3235888A3

Abstract

The invention relates to a method for producing a pressure-sensitive adhesive mass on the basis of at least one polymer, consisting in subjecting the at least one polymer to cross-linking, said polymer having functional groups Y. In addition, said polymer is mixed with at least one type of functionalized particles having at least one non-polymeric base unit. The invention is characterized in that the particles comprise a surface modification of the base unit, said surface modification of the particles having at least one type of functional groups X and the cross-linking of the polymer being at least partially achieved by a reaction of functional groups X with functional groups Y of the polymer. Also disclosed are pressure-sensitive adhesive masses based on at least one cross-linked polymer component, wherein the polymer component is at least partially cross-linked by the integration of functionalized particles, the particles comprising at least one non-polymeric base unit and a surface modification of said base unit, and wherein the surface modification of the particles has at least one type of functional groups X which are capable of reacting with functional groups Y present in the polymer component. The invention further relates to the use of surface-modified functionalized particles having a non-polymeric base unit as cross-linking reagents for cross-linking polymers for the production of pressure-sensitive adhesive masses.

Description

tesa AG

description

Pressure-sensitive adhesives and process for their preparation

The present invention relates to pressure-sensitive adhesives which can preferably be processed solvent-free and are distinguished not only by good processability and, in particular, coatability by good product properties. The invention encompasses the composition of novel PSA formulations, their preparation, processing and use in self-adhesive products. Furthermore, a novel concept is part of this invention, over which the combination of good processability and good product properties for such PSA formulations can be realized.

State of the art

In the field of adhesives, pressure-sensitive adhesives are distinguished in particular by their permanent tackiness. A material that has permanent tack must have a suitable combination of adhesive and cohesive properties at all times. This distinguishes it, for example, from reactive adhesives, which hardly provide cohesion in the unreacted state. For good product properties, it is necessary to adjust pressure-sensitive adhesives so that the balance of adhesive and cohesive properties is optimally balanced. This balance is typically achieved by converting polymer chains contained in PSA formulations into wide-meshed networks. The nature of the network has a decisive influence on the adhesive and cohesive properties of the PSA. Although a material with pronounced cross-linking shows good cohesion, the flexibility is reduced, so that the material can not sufficiently adapt to the roughness of a substrate surface. In addition, a material with pronounced cross-linking can only dissipate deformation energy to a lesser extent, as occurs under load. Both phenomena reduce the bond strength. On the other hand, although a slightly crosslinked material can flow well on rough surfaces and dissipate deformation energy so that the adhesion requirements can be met, the material is insufficiently resistant to stress due to reduced cohesion. One type of crosslinking that has an influence on the adhesion / cohesion balance is temporary polymer chain entanglements. However, these are sufficient only for a sufficient cohesion of the PSA, if the molecular weight of the polymers is sufficiently high. Pressure-sensitive adhesives based on natural rubbers can be based solely on this crosslinking principle. Further possibilities for adjusting the crosslinking of the PSA are chemical and thus irreversible crosslinking. Chemical crosslinking can also be achieved by radiation-chemical treatment of the PSAs. Furthermore, it is possible to use physical networking principles. Examples of such, typically thermoreversible crosslinks in PSAs are in thermoplastic elastomers such as in some block copolymers or semicrystalline polymers.

In addition to the mentioned crosslinking principles, fillers can also be used to increase the cohesion. Often, a combination of filler / filler interactions and filler / polymer interactions results in the desired reinforcement of the polymer matrix. A cohesion increase based on this represents another physical type of crosslinking.

For fillers which are mentioned in terms of a reinforcing effect in PSAs, in particular the class of fumed silicic acids may be mentioned. You will u. a. used as thickening agents, gelling agents or thixotropic agents in fluids of various kinds, with their influence on the theological

Properties of the fluids uses. The use of hydrophilic and hydrophobic

Silica described. Examples of the use of fumed silica in the field of pressure-sensitive adhesives are described in US 4,163,081 by Dow Corning, US 4,710,536

3M and described in DE 102 08 843 A1 by BASF AG.

Other fillers described in WO 02/81586 A1 by 3M, in WO 02/24756 A2 by Rohm & Haas and in JP 2002 167,557 by Sekisui describe the use of modified phyllosilicates for improving the product properties.

In all these cases, the reinforcement results from an influence of the particles on the elastic modulus of the elastomer composite. The interaction is caused by physical interactions between individual particles on the one hand and particles and polymers on the other hand. Often, however, these physical interactions are not sufficient to even small mechanical deformations, as for example when loading a PSA by shear or Peeling may occur, withstand. This nonlinear phenomenon is known as the Payne effect and manifests itself as elastic modulus loss under deformation. An overview of the description of this effect and various mechanistic explanations are given by Heinrich and Klüppel [G. Heinrich, M. Klüppel, Adv. Polym. Sci., 2002, 160, 1-44].

In the previous part, various examples of types of crosslinking have been given, such as can be used in PSAs for improving product properties, in particular cohesion. For each of these types of crosslinking, the question arises to what extent they have an influence on the processing properties and in particular the coating behavior. A related discussion will be made below.

In addition to the product properties and thus the optimum balance of adhesive and cohesive properties of a PSA, their processability is also of central importance. In general, processability is reduced by the crosslinking of a formulation. Mostly, processability even becomes impossible. It is therefore advantageous to carry out or initiate crosslinking only during or after processing, in particular during or after the coating. However, if the crosslinking state results from the mere existence of a constituent in the formulation, as is the case with the above-mentioned fillers, the processing behavior is impaired thereby. High molecular weight polymers also belong to formulation ingredients which, because of their entangled state, have advantageous product properties, but may be disadvantageous in processibility, also due to their entangled state. In both cases, that is, entanglements and fillers, the physical principles which lead to crosslinking of the PSA system and thus advantageous product properties have a negative effect on the processing behavior, in particular the coating barrier.

Classic approaches to circumvent this dilemma are based on the use of solvents as process tools. An increased environmental awareness and the

However, the desire for ever more efficient production methods justifies the trend towards solvent-free processes. Compared to solvent-containing processing methods, the polymer-based pressure-sensitive adhesive raw materials used in the so-called hotmelt

Process (hot melt process) in their melt through the entanglements and / or filler particles to a crosslinking state, with significantly higher viscosities and

Elasticities is connected. In contrast to physical types of crosslinking, chemical crosslinking methods offer the advantage that network formation can only be initiated by suitable process control during processing. However, the use of chemical crosslinkers is limited by their reactivity over the pot life. If the network forms too much before the material is coated, then the already increased elasticity will result in a deterioration of the processing properties, and lower quality coating images may result. A particular difficulty arises in solvent-free systems, since elevated temperatures are necessary for the processing, which at the same time leads to an acceleration of the chemical crosslinking reaction. An example of such a system is described in U.S. 4,524,104 by Sanyo. Radiation-crosslinking methods appear to be advantageous in this sense, since only after the coating network formation is specifically initiated, as proposed for example in EP 377 199 by BASF. However, to obtain networks with a structure that meets the later product requirements in terms of shear strength, again quite high molecular weight polymers are required, which in turn may have disadvantages in processing behavior by their Schlaufungszustand.

Typically, the processability of a material deteriorates with the increase in its elasticity. Network formation always leads to an increase of the memory module and thus higher elasticity. As a result, the flowability required for processing and coating deteriorates or even is completely lost. In the case of coating, inhomogeneities in the coating pattern up to melt fracture can then occur. Various authors describe this phenomenon, in particular for capillary and extrusion nozzles. Literature on this is in Pahl et al. [M. Pahl, W. Gleissle, H. -M. Laun, Practical Rheology of Plastics and Elastomers, 4th ed., 1995, VDI Verlag, Dusseldorf, p 191fJ and Tanner [R. I. Tanner, Engineering Rheology, 2nd ed., 2000, Oxford University Press, Oxford, p. 523fJ.

Therefore, systems are sought which are preferably coatable solvent-free and which have a combination of good product properties on the one hand - and in particular with respect to cohesion - and on the other hand show improved processing properties, in particular coatability.

A particularly advantageous example of systems which at least partially satisfy this combination of requirements are block copolymers containing segments which soften at high temperatures (the so-called hard phase) and others which are known in the art

Application temperature melted present. The softening temperature of the hard phase Due to the use of special monomers, it is typically adjusted in such a way that good product properties prevail at room temperature, but the material can be coated from the melt in a simple manner at process-technically sensible temperatures. Since these materials typically do not have high molecular weights, their melt viscosity and elasticity are comparatively low once the hard phase is softened.

A disadvantage of the above-mentioned PSAs based on block copolymers, however, is their thermal shear strength, which is limited by the softening of the hard domains which begins at elevated temperature. Another disadvantage is the complicated production conditions for block copolymers. In order to produce polymers with the required block-like structure in sufficient quality, controlled or living polymerization processes are required, which are sometimes expensive. In addition, not all monomer combinations are always feasible in a simple manner. On the one hand, the block copolymer approach is therefore not universally regarded as flexible for many polymer systems. On the other hand, there is a need for pressure-sensitive adhesives having better thermal resistance.

The aim of the present invention is therefore to provide a flexible concept which comprises a suitable combination of material and process, so that preferably solvent-free processable PSAs with good processing properties and good product properties can be produced.

As has now been found, this combination of requirements, consisting of good processability and good product properties, can be solved by providing a process for

Production of crosslinked PSAs is used, in which a special

Pressure-sensitive adhesive formulation contains such functionalized particles that the particles can be linked during or after the coating by the action of radiation energy, in particular electromagnetic radiation, particle radiation and / or thermal energy with at least one kind of polymeric constituents of the PSA formulation.

description

The present invention relates to a process for the preparation of a crosslinked PSA, crosslinked PSAs obtainable by such a process, and the use of such PSAs. Furthermore, the Intermediate products of such a process, in particular the composition of novel formulations for PSAs. The combination of the inventive novel PSA formulations with the preparation process according to the invention is likewise in accordance with the invention and a central component of this application (see also FIG. 1).

The invention relates to a method for producing a pressure-sensitive adhesive based on at least one polymer A, in which a crosslinking of the at least one polymer A is carried out, wherein the polymer has functional groups Y, wherein furthermore the polymer with at least one kind of functionalized particles B (hereinafter The particles have at least one non-polymeric base unit and a surface modification of this base unit, the surface modification of the base unit at least one kind of functional group X. According to the invention, the crosslinking of the polymer is at least partly due to a reaction of the functional groups X. of the particles and of the functional groups Y of the polymer The crosslinking can also be effected completely in the sense of the invention by means of the functionalized particles.

The subclaims relate to advantageous variants of the method according to the invention.

The invention further relates to a pressure-sensitive adhesive based on at least one crosslinked polymer component A, wherein the crosslinking of the polymer component A is effected at least in part by incorporation of functionalized particles B, the particles B having at least one non-polymeric base unit and a surface modification of this base unit, wherein the Surface modification of the particles B has at least one variety of functional groups X, which are able to react with functional groups Y present in the polymer component A.

In particular, it is intended to emphasize such a pressure-sensitive adhesive when it is obtainable by the process described as being according to the invention.

The invention additionally relates to the use of surface-modified particles with a nonpolymeric base unit, in particular of those particles described within the scope of this document, as crosslinking reagents of polymers for producing PSAs. Also considered to be in accordance with the invention are the not yet crosslinked polymers A which have been added with the functionalized particles B. Other components may be present in the PSA to be crosslinked.

The PSA formulations according to the invention contain at least one type of polymer A which contains at least one type of Y-type group and at least one type of filler particles B which contain at least one type of X-type group on the particle surface. For the purposes of this invention, groups of the Y type and the X type are selected such that a bond between at least one Y-type group and at least one X-type functional group is formed by the action of electromagnetic radiation, particle radiation and / or thermal energy An adduct of the type B-X'-Y'-A is formed (see Figure 2). The designation X indicates that the structure of the functional group X may have changed after the reaction has ended. Similarly, the designation Y indicates that the structure of the functional group Y may have changed after the reaction has been completed. It is also according to the invention if the functional groups X and Y have not changed in their structure, but nevertheless have entered a link.

In this description, the terms "electromagnetic radiation" and "particle radiation" are to be understood as all radiation forms which are summarized by VD McGinniss [VD McGinniss in Encyclopaedia of Polymer Science and Engineering, HF Mark, NM Bikales, CG Overberger, G. Menges ( Ed.), 2nd ed., 1986, Wiley, New York, Vol. 4, p. 418ff]. These radiation forms are preferably used according to the invention. Crosslinked PSAs are advantageously obtained by the novel use of the novel formulations described here in combination with the process described here. The functionalized filler particles B act as multifunctional crosslinkers. By virtue of its ability to combine several polymer chains at one crosslinking point, it is possible to reduce the molecular weight of the polymeric constituents of the PSA to be crosslinked (starting from polymeric constituents for the PSA which, based on conventional processes of the prior art, have a reduced molecular weight Have molecular weight). This is followed by an improvement in the processing behavior. Conversely, for the purposes of this invention, it is also possible to add pressure-sensitive adhesives containing crosslinkable polymers of low molecular weight to the filler particles according to the invention. After exposure to electromagnetic radiation, particle radiation and / or thermal energy, network structures other than if the filler particles of the invention were not present are obtained. This novel state of crosslinking is characterized by the fact that improved product properties, in particular an increased cohesion of the PSA, are correlated with it. It is typically characteristic of the novel crosslinking state that the adhesive properties of the PSAs according to the invention are at least at the level at which a crosslinked PSA is present which contains no filler particles according to the invention but has been processed in a comparable manner and has a comparable gel content.

Advantageously, the novel PSA formulations containing at least one grade of a polymer A according to the invention and at least one grade of a functionalized filler particle B have good processing properties in the raw state, ie before the beginning of the processing. For the purposes of this invention, the processing properties are in particular the viscosity of the PSA formulation and its elasticity. The viscosity is given as the zero viscosity η ₀ for different temperatures. It can be obtained from capillary viscosimetrically determined viscosity curves. The elasticity is given in the form of the first normal stress difference N ₁ , also at different temperatures. The data for the first normal voltage difference can also be obtained from capillary-viscometric experiments. Both sizes, the viscosity and the first normal stress difference, are generally shear rate dependent for PSA formulations. Thus, depending on the process and the shear rates involved, they can vary for a given PSA formulation. It is useful for the description of this invention, to limit itself to a shear rate, but without thereby limiting the inventively employable method in this regard. As such a shear rate, the shear rate of 1000 s ^{-1 is selected} as the representative preferable value. For the processability and especially the coatability, it is very advantageous if a certain ratio of elasticity and viscosity is not exceeded at the shear rate predetermined by the process. If this ratio is too high, the elastic character of the material to be coated predominates. As a result, melt fracture may occur, which manifests itself in an inhomogeneous line image (M.Pahl, W. Gleißle, H. -M. Laun, Practical Rheology of Plastics and Elastomers, 4th ed., 1995, VDI Verlag, Dusseldorf, p 191f).

According to the results of capillary-viscometric rheology, the ratio R = N ₁ /! from first normal voltage difference N ₁ and the shear stress τ the

Processing behavior of a polymer melt [W. Gleissle, Rheol. Acta, 1982. 21, 484 -

487; M. Pahl, W. Gleissle, H.-M. Laun, practical rheology of plastics and elastomers, 4th ed., 1995, VDI Verlag, Dusseldorf, p. 320ff]. The shear stress τ is given as the product of viscosity and shear rate. The numerator of the quotient N ₁ /! describes the elastic properties of the material, the denominator the viscous. The latter also shows the dependence on the process speed in the form of the shear rate in mind. Above a critical value for R, flow anomalies occur. If, therefore, at the shear rates prevailing during processing, it is possible to reduce N ₁ by a material concept or at least not to increase it further by additional crosslinking effects, then it is expected that the material can be coated without melt inhomogeneities. This can be done, for example, such that a crosslinking is initiated only after the coating, as is possible for example in a radiation-chemical treatment. The irradiated and thus crosslinked material has increased elasticity and, associated therewith, a higher first normal stress difference and could not be processed in this state with a good coating pattern. However, the non-crosslinked melt is less elastic, exhibits a lower first normal stress differential, and can be successfully coated. For PSAs having good cohesion, polymers having high molecular weights are often needed. However, these intermolecular interactions, such as entanglements, can already exhibit high elasticities in the chemically unvarnished state, which can lead to disadvantages in the coating behavior.

The novel concept according to the invention comprises that the cohesion of the pressure-sensitive adhesive of the invention is essentially achieved by an improved crosslinking state via chemical linking of polymers to filler surfaces. Therefore, a high molecular weight of the polymers is no longer absolutely necessary and consequently the coating behavior is less limited by chain entanglements. The particles themselves are present during processing as a disperse phase in the PSA formulation. Since they are not yet chemically linked to polymeric components of the formulation at this time, they only contribute incompletely to the elasticity of the formulation at this time. Only upon initiation of the crosslinking reaction during and / or after coating does the desired cohesion be generated. The requirements of the pressure-sensitive adhesive formulations according to the invention are that the formulation in the non-crosslinked state is given a good processibility, for example by a low first normal stress difference, and in particular the ratio R, and in the crosslinked state a good cohesion, for example by shearing life or Gel content of a self-adhesive tape specimen, must be distinguished. Advantageous PSAs according to the invention which are obtained via the coating and crosslinking process according to the invention have, compared to a formulation which has been coated and crosslinked in the same way, but contains no filler particles according to the invention, but has a comparable gel fraction (test B), typically at least 50 %, preferably increased by at least 100% shear time after test D. The adhesion, given by the bond strength according to test C, is typically at least at the same level as the adhesion of the aforementioned reference system for the PSA system according to the invention, or is preferably at least 25% higher. At the same time, the R value of the pressure-sensitive adhesive according to the invention in the unvemetted state at a material-specific suitable temperature between 25 ° C. and 300 ° C., also in comparison with a formulation which contains no filler particles according to the invention and is also uncrosslinked, hardly increases and remains at values of preferably at most R = 3.5 (test A2). The viscosity of the PSAs of the invention is not or only slightly at the same temperature, preferably up to at most 25%, higher than that of a formulation which contains no filler particles according to the invention and is also uncrosslinked (test A1).

Composition of PSA Compositions According to the Invention

The PSA formulations according to the invention comprise at least one type of polymer A and at least one type of filler particle B, wherein the at least one polymer grade A has groups Y present therein with groups X which are on the surface of the at least one filler particle type B, by the action of electromagnetic radiation, of particle radiation and / or thermal energy during and / or after a coating. The pressure-sensitive adhesive of the invention may optionally contain further constituents other than polymers A and filler particles B. In this section, reference is made to the polymers A according to the invention, the fillers B according to the invention and further constituents which can optionally be used in the PSA formulations according to the invention and the nature of the groups X and Y are described.

The PSAs according to the invention advantageously contain up to 50% by weight of at least one filler particle type B, preferably up to 20% by weight, very preferably up to 12% by weight. Polymers A

The at least one type of polymer A is then preferred according to the invention if it has a molecular weight of not more than 10,000,000 g / mol, preferably not more than 500,000 g / mol. Furthermore, the at least one polymer grade A preferably has a softening temperature of less than 100 ° C., more preferably less than 20 ° C. The at least one type of polymer A may be of linear, branched, star or grafted structure, to give only a few examples, and constructed as a homopolymer or random copolymer. The term "random copolymer" for the purposes of this invention includes not only those copolymers in which the comonomers used in the polymerization are purely randomly incorporated, but also those in which occur gradients in the comonomer composition and / or local enrichment of individual Comonomersorten in the polymer chains ,

The molecular weight in this context is the weight average molecular weight distribution, as it is accessible, for example, via gel permeation chromatographic investigations. Softening temperature in this context means the glass transition temperature for amorphous systems and the melting temperature for semicrystalline systems, which can be determined for example by dynamic differential scanning calorimetry (DSC). If numerical values for softening temperatures are given, then in the case of amorphous systems these relate to the mid-point temperature of the glass step and, in the case of semicrystalline systems, to the temperature with maximum exotherm during the phase transition.

It is also possible within the meaning of this invention that the at least one type of polymer A is a block copolymer. Particularly advantageous are those block copolymers in which preferably each of the occurring blocks (independently of one another) has a molecular weight of less than 1,000,000 g / mol, preferably less than 250,000 g / mol, of linear, branched, star-shaped or grafted structure and / or constructed as a homopolymer or random copolymer. Furthermore, at least one type of block advantageously has a softening temperature of less than 100 ° C., preferably less than 20 ° C. The individual block types occurring in the block copolymer may differ with regard to the comonomer composition and optionally in terms of their molecular weight and / or softening temperature and / or structure (for example of a linear or branched type). The different polymer arms in star-shaped and grafted systems can be of different chemical nature, that is to say consist of different monomers and / or different

Comonomer composition.

Polymers of grade A are furthermore preferred according to the invention if they contain at least one type of group Y which contains groups X which are located on the surface of the at least one type of filler particle B under the influence of electromagnetic radiation, particle radiation and / or thermal energy or connect after a coating. The groups of the at least one type Y can be present in a variety of ways in the at least one type of polymer A. The at least one type of polymer A may for example be constructed as a homopolymer of monomers containing at least one kind of groups Y. Further, the at least one type of polymer A may also be constructed as a random copolymer obtained from at least one kind of monomers containing at least one kind of groups Y and optionally one or more kinds of monomers not containing such groups. It is also possible that the at least one type of polymer A contains the at least one sort of groups Y only at individual points along the polymer backbone. Examples of such embodiments include groups located at chain ends, in the range of chain or block centers, in the range of branch points, or in the range of block junctions. Polymers of the at least one type A are then particularly preferred according to the invention if the polymer molecule contains on average at least two such groups. It is also possible that the at least two groups Y are introduced into the at least one polymer A via a grafting reaction. It is likewise according to the invention to introduce the at least two groups Y into the at least one polymer type A by carrying out a polymer-analogous reaction. In addition, any combinations of the mentioned types of functionalization are according to the invention.

As examples of polymers A, but without wishing to make any restriction, the following homopolymers and random copolymers are mentioned as being advantageous for the purposes of this invention: polyethers, such as, for example, For example, polyethylene glycol, polypropylene glycol or polytetrahydrofuran, polydienes, such as. As polybutadiene or polyisoprene, hydrogenated polydienes such. As polyethylene butylene or polyethylene propylene, rubbers, such as. As natural rubber, nitrile rubber or chloroprene rubber, butadiene-containing rubber, isoprene-containing rubber, polyisobutylene, polyolefins, such as. Ethylene homopolymers or copolymers, propylene homopolymers or copolymers, metallocene catalyzed polyolefins, polysiloxanes, polyalkyl vinyl ethers, polymers of unfunctionalized α, β-unsaturated esters, copolymers based on α, β-unsaturated esters, copolymers based on alkyl vinyl ethers and ethylene-vinyl acetate copolymers, EPDM rubbers and styrene-butadiene rubbers. Further advantageously usable random copolymers are obtained by copolymerization of isoprene and / or butadiene, have 1,4-, 1,2- and / or 3,4- or 1,4- and / or 1,2-incorporation of the monomers in the polymer chain and may be fully or partially hydrogenated.

Particularly advantageous for the purposes of this invention are random copolymers based on unfunctionalized α, ß-unsaturated esters. If these are used for the at least one type of polymer A with a copolymer character, then, in principle, all the compounds which are familiar to the person skilled in the art and are suitable for the synthesis of polymers can be used as monomers in their preparation. Preference is given to α, β-unsaturated alkyl esters of the general structure

CH ₂ = CH (R ¹ XCOOR ² ) (I)

wherein R ¹ = H or CH ₃ and R ² = H or linear, branched or cyclic, saturated or unsaturated alkyl radicals having 1 to 30, in particular having 4 to 18 carbon atoms.

Monomers which are very preferably used in the sense of general structure I for polymers A with a copolymer character include acrylic and methacrylic acid esters having alkyl groups consisting of 4 to 18 C atoms. Specific examples of such compounds are, without being limited by this list, n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-heptyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-nonyl methacrylate, n-decyl acrylate, n-decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, their branched isomers such as e.g. As sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and iso-octyl acrylate and cyclic monomers such. Cyclohexyl acrylate, cyclohexyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate and isobornyl methacrylate.

Also useful as monomers for polymers A copolymer character are acrylic and methacrylic acid esters containing aromatic radicals such. Phenyl acrylate, benzyl acrylate, benzoin acrylate, phenyl methacrylate, benzyl methacrylate or benzoin methacrylate. Furthermore, ethoxylated and propoxylated acrylates and methacrylates can be used according to the invention. In such systems, the acrylate or methacrylate side chain is formally made of an oligomer or polymer of ethylene oxide or propylene oxide.

Furthermore, vinyl monomers, vinyl ethers, vinyl ethers, vinyl halides, vinylidene halides, as well as vinyl compounds containing aromatic cycles and heterocycles in α-position can optionally be used. Examples of monomers which may be used according to the invention for the optionally usable vinyl monomers are: vinyl acetate, vinylformamide, vinylpyridine, ethylvinylether, 2-ethylhexylvinylether, butylvinylether, vinylchloride, vinylidenechloride, acrylonitrile, styrene, .alpha.-methylstyrene.

In a preferred embodiment of this invention, the at least one type of polymer A contains its at least two groups Y in the form of at least one particular comonomer which has been randomly copolymerized during polymerisation of the polymer. In this case, the molar fraction of this at least one particular comonomer with respect to the composition of the total monomer mixture in the production of the total polymer is up to 50 wt .-%, preferably up to 20 wt .-%, very preferably up to 5 wt .-% , The special character of this at least one comonomer is that it carries at least one group Y, which contains at least one group X, which is located on the surface of the at least one filler particle type B, under the influence of electromagnetic radiation, particle radiation and / or thermal energy during or after a coating can form a connection. Examples of groups X and Y are described in the section "Combinations of Groups X and Y". Particular preference is given to using monomers based on α, β-unsaturated esters which contain these groups. It is also possible that groups Y are linked via a polymer-analogous reaction with the polymer A at the sites where these particular comonomers are incorporated. It is also possible that these particular comonomers are derivatized prior to polymerization with groups Y, ie that comonomers having not necessarily inventive functionalization prior to polymerization and thus producing a type A polymer with a chemical moiety is modified via which at least one group of the invention Y is incorporated into the comonomer and after this modification reaction and subsequent polymerization for the formation of a linkage according to the invention with at least one group X available. Examples of comonomers bearing functional groups include, but are not limited to, allyl acrylate, allyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4- Hydroxybutyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylated benzophenone, methacrylated benzophenone, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, N-tert-butylacrylamide, N-tert- Butylmethacrylamid, N-iso-propylacrylamide, N-iso-propylmethacrylamide, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, acrylic acid, methacrylic acid, vinyl alcohol, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether and allyl glycidyl ether called.

If the at least one type of polymer A is a block copolymer, then in the simplest case diblock copolymers of the form PA-PA consisting of a block PA and a block PA which differ with respect to the selected starting monomers and optionally in their softening temperature and / or molar mass and / or structure (eg of a linear or branched type) may be different. Further embodiments of polymers A of block copolymer character are, without intending to limit, triblock copolymers of the type PA-PA'-PA ", block copolymers of the type PA-PA'-PA" PA '"and higher block copolymers whose structures continue this series. Triblock copolymers and higher block copolymers are then according to the invention in the sense of polymers A with block copolymer character, if all directly linked blocks with respect to the selected starting monomers and optionally in their molecular weight and / or softening temperature and / or structure (eg linear or branched type Further, triblock copolymers and higher block copolymers are according to the invention in the sense of the polymers A, if several of the blocks not directly linked to one another are selected with respect to the selected starting monomers and optionally in their molecular weight and / or softening temperature and / or structure (eg or branched type) are not different from each other. A preferred design of a block copolymer-type polymer A is a triblock copolymer of the type PA-PA'-PA "wherein PA and PA" are the same with respect to the selected starting monomers, molecular weight, softening temperature and structure. The block linkage in polymers A of block copolymer character may be in a linear form, but also in a star-shaped form or as a graft copolymer variant. Each individual block can be constructed as a homopolymer block or copolymer block. Thus, for the blocks, the definitions as set forth in the section "Homopolymers" and "Statistical Copolymers" apply. If a block copolymer is used as polymer A, then preferably at least one block type will contain type Y functionalizations. Particularly preferred are diblock copolymers which contain Y type functionalizations in only one block type, symmetric triblock copolymers containing Y type functionalizations in both end blocks only Triblock copolymers containing only type Y functionalities in the middle block.

Filler particles B

When the at least one filler B in the meaning of this invention are preferably those filler particles for use in which comprise the basic units without surface modifications softening temperatures greater than 200 ° C, preferably greater than 500 ⁰ C. There are also such systems, the softening temperature (based on the unmodified base units) above the decomposition temperature, then according to the invention, when the decomposition temperature is above 200 ⁰ C, preferably above 500 ⁰ C.

The materials on which the base unit of the at least one filler particle type B is based may be inorganic in nature or may be an inorganic / organic hybrid material and have an amorphous, semi-crystalline or crystalline character. Also, base units of organic nature can be used in accordance with the invention.

The filler particles may preferably be spherical, rod-shaped or platelet-shaped in structure. Separated particles, often called primary particles, are just as well according to the invention as aggregates formed from a plurality of primary particles. Such systems often show a fractal superstructure. If the particles are formed from crystallites, then the primary particle shape depends on the type of crystal lattice. Platelet-shaped systems can also be present in the form of layer stacks.

In an advantageous embodiment of this invention, the at least one functionalized filler type is present in the PSA essentially in the form of singular spherical particles. The particle diameters then have values of less than 500 nm, preferably less than 100 nm, very preferably less than 25 nm. In a further advantageous embodiment of this invention, the at least one functionalized filler in the PSA is substantially in the form of singular platelet-shaped particles. The layer thickness of such platelets then has values of preferably less than 10 nm and a maximum diameter of preferably less than 1000 nm. In a further advantageous embodiment of this invention, the at least one filler in the PSA is substantially in the form of singular rod-shaped particles. In this case, these rods have a diameter of less than 100 nm and a length of less than 15 microns. The rods may also be curved and / or flexible. Furthermore, it is advantageously possible for the purposes of this invention that the at least one filler type is present in the PSA in the form of primary particle aggregates. These aggregates have a radius of gyration (analogous to the term "gyration radius" known by polymers) of less than 1000 nm, preferably less than 250 nm. Particular preference is given to using those filler particles in the sense of this invention whose spatial extent in at least one direction is less than 250 nm, preferably less than 100 nm, very preferably less than 50 nm. It is also possible within the meaning of this invention to use combinations of the above to use the mentioned filler types.

Typical and inventively advantageous classes of compounds which make up the base unit of the at least one filler particle type B are oxides of inorganic nature - in particular metal oxides and / or semimetal oxides - salts of alkaline earth metals and silicates-based minerals, in particular clay minerals and clays. The amorphous or crystalline metal oxides which can be used according to the invention include, for example, silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide and zinc oxide. The skilled worker is familiar with other systems which can also be used according to the invention. Alkaline earth metal salts include, for example, carbonates, sulfates, hydroxides, phosphates and hydrogen phosphates of magnesium, calcium, strontium and barium. Silica systems such as serpentines, kaolins, talc, pyrophyllite, smectites, in particular montmorillonite, vermiculites, illites, mica, spiked mica, chlorites, sepiolite and palygorskite, are among the clay minerals and clays that can be used according to the invention. Furthermore, synthetic clay minerals such as hectorites and their related systems such. B. Laponite ® Fa. Laporte and Fluorhectorite and their related systems such. B. Somasif ® Fa. Co-Op are used according to the invention.

The at least one type of filler particle B is surface-modified. Typical surface modification reagents which are advantageous according to the invention are organosilanes and surfactants, but also organotitanium compounds, fatty acids or polyelectrolytes, such as, for example, short-chain polymers having a high acrylic acid content. The function of these surface modification reagents is, above all, compatibility of the Particle surface with the matrix in which they are to be dispersed to create. As another object, surface modification reagents are used to prevent coalescence of smaller particles into larger objects. Very advantageous in the sense of the invention, at least one type of surface modification reagent is used which, in addition to the compatibilizing and anti-aggregation function, also offers the possibility of connecting at least one group Y via at least one group X incorporated in the at least one kind of surface modification reagent , which is contained in at least one type of polymer A, to undergo exposure to electromagnetic radiation, particle radiation and / or thermal energy during or after a coating. A filler particle preferably carries on its surface at least 10 groups of at least one kind X, more preferably at least 50.

Filler particles containing in their native form (in the form of the non-surface-modified base unit) on the surface hydroxide groups, preferably offer the possibility of a reaction with chlorosilanes or alkoxysilanes. Following hydrolysis of the silane, condensation of silanol groups with the hydroxide groups on the particle surface takes place. If at least one substituent on the central silicon atom of the silane is an organic radical, then in the case of complete surface coverage with silane molecules, an organophilic shell is covalently linked to the filler particle and thus the particles are provided with polymer matrix compatibility. The concepts and typically used classes of materials that can be used in the context of this invention, z. As described by R.N. Rothon [R. N. Rothon (ed.), "Particulate-Filled Polymer Composites", 2nd ed., 2003, Rapra Technology, Shawbury, 153-206].

For the purposes of this invention, two classes of silanes can be distinguished, in particular those which, in addition to the groups which are capable of reacting with the base surface, carry exclusively organic radicals which are chemically inert (see structure II), and others which contains, in addition to the groups capable of reacting with the base surface, at least one organic radical bearing at least one group X which is a compound having at least one group Y contained in at least one type of polymer A under the action of electromagnetic radiation Radiation, of particle radiation and / or thermal energy during or after a coating can enter (see structure III). In silane II, at least one of the substituents A, B, D represents a hydrolyzable group, that is, for example, a chlorine atom or an alkoxy group. At least one of the substituents B, C, D represents an organic Rest consisting of a linear, branched or cyclic hydrocarbon, which may also be aromatic and of low molecular weight, oligomeric or polymeric nature. If more than one hydrolyzable group is present among the substituents A, B, D, then these may be of the same or different chemical nature, all of which correspond to the definition above for hydrolyzable groups. If more than one organic radical is present among the substituents B, C, D, these may also be of the same or different chemical nature, all of which correspond to the definition above for organic radicals. In silane IM, at least one of the substituents A, E, F represents a hydrolyzable group, that is, for example, a chlorine atom or an alkoxy group. At least one of the substituents E, F, G represents an organic radical consisting of a linear, branched or cyclic hydrocarbon which may also be aromatic and of low molecular weight, oligomeric or polymeric nature and which additionally contains at least one group X containing a compound with at least one group Y, which is contained in at least one type of polymer A, under the influence of electromagnetic radiation, can enter into particle radiation and / or thermal energy during or after a coating. If more than one hydrolyzable group is present among the substituents A, E, F, then these may be of the same or different chemical nature. If more than one organic radical is present among the substituents E, F, G, these may also be of the same or different chemical nature, all of which correspond to the definition above for organic radicals.

B E

A-Si-C (II) A-Si-G (IM)

D F

Advantageous designs of silanes of the structure II which can be used according to the invention are those in which only A is used as the hydrolyzable group and B, C, D are organic radicals of which B and D have the same chemical nature and C are of a different chemical nature. Further advantageous embodiments of silanes of the structure II which can be used according to the invention are those in which A and B are used as hydrolyzable groups of the same chemical nature and C and D are organic radicals which are of the same chemical nature. Further advantageous embodiments of silanes of the structure II which can be used according to the invention are those in which A, B, D are used as hydrolyzable groups of the same chemical nature and C is an organic radical.

Advantageous embodiments of silanes of the structure IM which can be used according to the invention are those in which only A is used as hydrolyzable group and E, F, G are organic radicals of which E and F are of the same chemical nature and G of a different chemical nature. G contains the at least one group X, which can form a compound with at least one group Y, which is contained in at least one type of polymer A, under the influence of electromagnetic radiation, particle radiation and / or thermal energy during or after a coating. Further advantageous embodiments of silanes of the structure IM which can be used according to the invention are those in which A, E, F are used as hydrolyzable groups of the same chemical nature and G is an organic radical containing the at least one group X which is a compound having at least one group Y. , which is contained in at least one type of polymer A, under the influence of electromagnetic radiation, can enter into particle radiation and / or thermal energy during or after a coating contains.

Hydrolyzable groups A, B, D, E, F, which may advantageously be used in silanes II and silanes III, are halogen atoms, in particular chlorine, and / or alkoxy groups, such as, for example, methoxy, ethoxy, n- Propoxy, iso-propoxy, n-butoxy, sec-butoxy or tert-butoxy groups. Furthermore, acetoxy groups can be used. The other examples of hydrolyzable groups known to the person skilled in the art are likewise usable in the context of this invention.

The organic radicals B, C, D, E, F, which can be used in silanes II and silanes M1, include, for example, without being exhaustive, methyl, ethyl, n-propyl, iso-propyl , n-butyl, sec-butyl, tert-butyl groups, pentyl groups and the branched isomers, hexyl groups and the branched isomers, heptyl groups and the branched isomers, octyl groups and the branched isomers, Nonyl groups and the branched isomers, decyl groups and the branched isomers, undecyl groups and the branched isomers, dodecyl groups and the branched isomers, tetradecyl groups and the branched isomers, hexadecyl groups and the branched isomers, octadecyl Groups and the branched isomers and eicosyl groups and the branched isomers. The organic radicals according to the invention may additionally contain ring-shaped and / or aromatic components. Representative structures are cyclohexyl, phenyl and benzyl groups. It is also according to the invention, when used as at least one organic radical oligomers or polymers containing at least one hydrolysable SiIyI group.

To the organic radicals E, F, G, in which at least one group X, which is a compound having at least one group Y, which is contained in at least one type of polymer A, under For example, the compounds listed in the list below (the list is not exhaustive) include: exposure to electromagnetic radiation, particle radiation and / or thermal energy during or after a coating: methyl, ethyl, n-propyl , isopropyl, n-butyl, sec-butyl, tert-butyl groups, pentyl groups and the branched isomers, hexyl groups and the branched isomers, heptyl groups and the branched isomers, octyl groups and the branched isomers, nonyl groups and the branched isomers, decyl groups and the branched isomers, undecyl groups and the branched isomers, dodecyl groups and the branched isomers, tetradecyl groups and the branched isomers, hexadecyl groups and the branched Isomers, octadecyl groups and the branched isomers and eicosyl groups and the branched isomers. The organic radicals according to the invention may also contain annular and / or aromatic components. Representative structures are cyclohexyl, phenyl and benzyl groups. It is further according to the invention, when used as at least one organic radical oligomers or polymers containing at least one hydrolyzable silyl group. If one remainder of the above list is used as one or more of the radicals E, F, G, then this is additionally modified by a chemical component which contains at least one group X.

For the purposes of this invention, preferably usable examples of silanes having structure II are methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, iso-butyltrimethoxysilane, iso-butyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane iso-, iso-octyltriethoxysilane, hexadecyltrimethoxysilane , Hexadecyltriethoxysilane, octadecylmethyldimethoxysilane, phenyltrimethoxysilane,

Phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane.

An example of silyl-functionalized oligomers or polymers that can be used according to the invention is polyethylene glycol, which is linked to a trimethoxysilane group.

For the purposes of this invention, particularly preferably usable silanes with structure IM, which carry at least one functionalization, are, for example, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, (N-butyl) -3-aminopropyltrimethoxysilane, 3- (N -ethylamino) -2-methylpropyltrimethoxysilane, 4-amino-3,3- dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyldimethoxymethylsilane, (N-

Cyclohexyl) aminomethyldinnethoxynethylsilane, (N-cyclohexyl) aminomethyltrinnethoxysilane, (N-phenyl) -3-aminopropyltrimethoxysilane, (N-phenyl) aminomethyldimethoxymethylsilane, (N-benzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, [2- (N Benzyl-N-vinylamino) -ethyl] -3-aminopropyltrimethoxysilane hydrogen chloride, [2- (N-benzyl-N-vinylamino) -ethyl] -3-aminopropyltrimethoxysilane, bis (3-propyltriethoxysilyl) -amine, vinyltrimethoxysilane,

Vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriisopropoxysilane,

Vinyldimethoxymethylsilane, vinyltriacetoxysilane, 3

Triethoxysilylpropylsuccinic anhydride, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3

Glycidyloxypropyldiethoxymethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-

Methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriisopropoxysilane, 3

Methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyloxypropyldiethoxynethylsilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane,

Isocyanatomethyltrimethoxysilane, isocyanatomethyldimethoxymethylsilane, tris [3-

(trimethoxysilyl) propyl] isocyanurate, 3-ureidopropyltrinnethoxysilane, 3

Ureidopropyltriethoxysilane, 2-hydroxy-4- (3-triethoxysilylpropoxy) benzophenone, 4- (3'-chlorodimethylsilylpropoxy) benzophenone, 3-mercaptopropyltrinnethoxysilane, 3-mercaptopropyldimethoxymethylsilane, bis (3-triethoxysilylpropyl) disulfane, bis (3- triethoxysilylpropyl) tetrasulfane, bis (triethoxysilylpropyl) polysulfan,

Octadecylaminodimethyltrinnethoxysilylpropylannnnoniunnchlorid.

Silanes disclosed in WO 00/43539 by Biochip Technologies or in EP 281 941 B1 by Ciba Geigy, and those disclosed by Kolar et al. [A. Kolar, H.F. Gruber, G. Greber, JMS Pure Appl. Chem., 1994, A31, 305-318], can also be used for the purposes of this invention as silanes having the structure IM. Similarly, organotitanium compounds can be used, which optionally can be done in conjunction with silanes.

It is likewise advantageous according to the invention if silanes of structure III are used which are derivatized with a chemical structural unit which contains at least one group X. This is to be understood as meaning that silanes of the structure III with nonfunctional functionalization before and / or after the surface modification reaction with the filler particles with a chemical unit via which the at least one group X according to the invention is introduced into the silane and after this silane modification reaction and the surface modification reaction to Forming a connection with at least one group Y is available modified.

The surface modification can be done completely by at least one representative of the silanes III. But it is also possible to use a combination of silanes IM and silanes II. Such a combination is then according to the invention, if at least 1 wt .-%, preferably at least 5 wt .-% of at least one representative of the silanes IM are used.

Silanes are particularly preferably used in the context of this invention as surface modifiers when filler particles are used which carry hydroxy groups on the surface at least in the state of the non-surface-modified base unit.

Examples of such filler particle types are metal oxides, in particular amorphous

Silica. An exemplary way of realizing a surface modification is given by Bauer and colleagues [F. Bauer, H. Ernst, U. Decker, M. Findeisen, H. -J. Gläsel, H. Langguth, E. Hartmann, R. Mehnert, C. Peuker, Macromol. Chem. Phys., 2000, 201, 2654 -

2659] and Rothon [R. N. Rothon (ed.), Particulate Filled Polymer Composites, 2nd ed.,

2003, Rapra Technology, Shawbury, pp. 153-206].

Particles which carry ionic groups on the surface in the state of the non-surface-modified base unit can preferably be modified with surfactants and / or fatty acids.

As surfactants, it is generally possible to use all quaternary ammonium compounds, protonated amines, organic phosphonium ions and aminocarboxylic acids, which exhibit amphiphilic behavior. It is advantageous to use ammonium compounds which carry at least three organic radicals, for example alkylammonium salts, trimethylalkylammonium salts, dimethyldialkylammonium salts, methylbenzyldialkylammonium salts, dimethylbenzylalkylammonium salts or alkylpyridinium salts. It is also possible to use alkoxylated quaternary ammonium compounds.

Two classes of surfactants can be distinguished within the meaning of this invention, on the one hand, which, in addition to the groups which are capable of interaction with the base surface, carry exclusively organic radicals which are chemically inert (see structure IV), on the other hand, which, in addition to the groups which are capable of linking to the base surface, contain at least one organic radical bearing at least one group X which is a compound having at least one group Y which is contained in at least one type of polymer A, under the action of electromagnetic radiation , from Particle radiation and / or thermal energy can enter during or after a coating (see structure V). In surfactant IV, the substituents A, B, D may be independently of one another organic radicals or hydrogen, the substituent C is a long-chain organic radical. As counterions, any anions may be used. Examples are chloride, bromide, hydrogen sulfate, dihydrogen phosphate and tetrafluoroborate. The person skilled in the art is aware of other substances which can likewise be used in the context of this invention. The organic radicals may independently of one another be linear or branched, saturated or unsaturated, be composed of aliphatic, olefinic and / or aromatic elements and contain 1 to 22 carbon atoms. Typical substituents used as organic radicals include methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, linear ones or branched pentyl groups, linear or branched hexyl groups, linear or branched heptyl groups, linear or branched octyl groups, benzyl groups or groups with higher numbers of carbon atoms. Preferred long-chain organic radicals are dodecyl groups, tetradecyl groups, hexadecyl groups, octadecyl groups or eicosyl groups in saturated or unsaturated form. Since the educts of surfactant production are often natural products, one finds only rarely chain-pure alkyl substituents. Rather, a mixture of different lengths of AI ky I chains is often present. Particularly preferred long-chain organic radicals are tallow radicals (unsaturated) or hydrogenated tallow radicals (saturated). It is also according to the invention that the surfactant function is carried out by oligomers or polymers which are functionalized so that they carry at least one cationic group.

B F

A - N - C (IV) E - N - C (V)

D G

Examples which may preferably be used as surfactants of structure IV for the purposes of this invention are hexadecyltrimethylammonium chloride or bromide, methylditaluminum ammonium chloride or bromide, the tallow radicals being saturated or unsaturated, dimethyltallowbenzylammonium chloride or bromide, the tallow If saturated or unsaturated radicals can be present, dimethyl tallow (2-ethylhexyl) ammonium chloride or bromide, where the tallow radicals may be saturated or unsaturated, dimethylditalgammonium chloride or bromide, where the tallow radicals may be saturated or unsaturated. Surfactants disclosed in EP 900 260 B1 by Akzo Nobel, US 5,739,087 by Southern Clay, US 5,718,841 by Rheox, US 4,141,841 by Procter & Gamble and by H. Grossmann [H. Großmann in catalysts, surfactants and mineral oil additives, H. Falbe, U. Hasserodt (eds.), 1978, G. Thieme, Stuttgart, p. 135ff] are disclosed, can also be used in the sense of this invention as surfactants having the structure IV.

Advantageous designs of surfactants of structure V which can be used according to the invention are those in which the substituents E, F, G independently of one another may be organic radicals or hydrogen and the substituent C is a long-chain organic radical. As counter ions any anions can be used. Examples are chloride, bromide, hydrogen sulfate, dihydrogen phosphate and tetrafluoroborate. The organic radicals may independently of one another be linear or branched, saturated or unsaturated, be composed of aliphatic, olefinic and / or aromatic elements and contain from 1 to 22 carbon atoms. Typical substituents used as organic radicals include methyl groups, ethyl groups, n-propyl groups, iso-propyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, linear or branched pentyl groups, linear or branched hexyl groups, linear or branched heptyl groups, linear or branched octyl groups, benzyl groups or groups with higher numbers of carbon atoms. Preferred long-chain organic radicals are dodecyl groups, tetradecyl groups, hexadecyl groups, octadecyl groups or eicosyl groups in saturated or unsaturated form. Natural products are also frequently used in the educts of the preparation of the surfactants V, with the result that seldom chain-pure alkyl substituents, but rather a mixture of different lengths of alkyl chains, are present. Particularly preferred long-chain organic radicals are tallow radicals (unsaturated) or hydrogenated tallow radicals (saturated). It is also according to the invention that the surfactant function is carried out by oligomers or polymers which are functionalized so that they carry at least one cationic group. In the case of the surfactants V, at least one of the substituents E, F, G, C contains at least one group X which contains a compound having at least one group Y which is contained in at least one polymer type A under the action of electromagnetic radiation, particle radiation and / or thermal Energy during or after a coating can go. Surfactants described in EP 900 260 B1 by Akzo Nobel, US 5,739,087 by Southern Clay, US 5,718,841 by Rheox, US 4,141,841 by Procter & Gamble and by H. Grossmann [H. Großmann in catalysts, surfactants and mineral oil additives, H. Falbe, U. Hasserodt (eds.), 1978, G. Thieme, Stuttgart, p. 135ff] are disclosed, can also in the sense of this Invention as surfactants having the structure V are used, as long as they are modified with at least one group X under certain circumstances, in addition to the disclosed structure.

Examples which may preferably be used for the purposes of this invention as surfactants of structure V are methyl tallow di- (2-hydroxyethyl) ammonium chloride or bromide, allyldimethyltetradecyl chloride or bromide, allyldimethylhexadecylammonium chloride or bromide, allyldimethyloctadecylammonium chloride or bromide.

For the purposes of this invention, it is preferably possible to use a combination of surfactants IV and surfactants V. In this embodiment of the invention are representatives of the surfactants

V to at least 1 wt .-%, preferably at least 5 wt .-% of all surfactants used. Furthermore, surfactants IV or V can be used in combination with cationic compounds which are themselves not surfactants but carry at least one group X which contains a compound having at least one group Y which is contained in at least one polymer type A under the action of electromagnetic radiation. Particle radiation and / or thermal energy can enter during or after a coating. At least 1 wt .-%, preferably at least 5 wt .-% of such a cationic compound according to the invention in combination with surfactants IV and / or

V used. If such cationic compounds are used, the sum of surfactants IV used and surfactants V is at most 99% by weight, preferably at most 95% by weight, it being possible for surfactants V to be completely replaced by surfactants IV. Examples of such cationic compounds are (2-acryloyloxyethyl) (4-benzoylbenzyl) -dimethylammonium chloride or bromide, 3-trimethylammoniumpropylmethacrylamide, chloride or bromide, 2-trimethylammoniumethyl methacrylate, chloride or bromide, 3-dimethylalkylammoniumpropylmethacrylamide, chloride or bromide, 2-dimethylalkylammonium methylmethacrylate Chloride or bromide.

Surfactants are particularly preferably used in the context of this invention when filler particles are used which have negative charges or partial charges on the surface (in the state of the non-surface-modified base unit). Examples of such filler particle types are some clay minerals, in particular smectites, in which intercalated cations can be replaced by surfactants. A principle of how such an exchange can take place is formulated by Lagaly [G. Lagaly in Tonminerale and Tone, K. Jasmund, G. Lagaly (ed.), 1993, Steinkopff, Darmstadt, p. 366ff].

It is also possible to use combinations of silanes according to the invention and surfactants according to the invention. At least one of the surface modification Reagents contain at least one group X capable of bonding with at least one group Y present in the polymer grade A under the action of electromagnetic radiation, particle radiation and / or thermal energy during or after coating.

Other ingredients

It is also according to the invention, optionally polymers C, which contain at least one group of the type X, and / or polymers C, which contain at least a group X and at least a group of the type Y, and / or polymers C, which neither groups of the type X still type Y, use. For the composition of those optional polymers which do not contain X or Y groups, the same information as to the structure, composition, choice of monomers, softening point and structure as defined in the definition of the polymers A applies, except the statements made there with regard to the Y groups. For optionally usable polymers which contain at least one group X, the statements made for polymers A apply, but such polymers C contain groups of the type X and not groups of the type Y and can therefore contain at least one group Y of the at least one polymer the variety A by the action of electromagnetic radiation, particle radiation and / or thermal energy during or after a coating form a connection. For the incorporation of the groups X in polymer C, the same statements made for the groups Y in the polymers A apply. If polymers carrying groups X and Y are used, the same information as regards composition, composition, choice of monomers, softening temperature and structure, as found in the definition for polymers A, but extended by the addition that additionally at least one group X is contained in the polymer. For the incorporation of the groups X and Y in polymers C, which bear both types of groups, the same statements made for the groups Y in the polymers A apply.

Other constituents which may be used are the PSA formulations according to the invention, tackifier resins, plasticizers, rheologically active additives, catalysts, initiators, stabilizers, compatibilizers, coupling reagents, crosslinkers, antioxidants, other anti-aging agents, light stabilizers, flame retardants, pigments, dyes, further fillers, in particular those which are not included in the include at least one type of filler particle B, and / or include blowing agent. Combinations of groups X and Y

The PSAs according to the invention contain at least one polymer grade A and at least one filler particle type B. Polymers A contain at least two groups Y, filler particles B contain at least one kind of groups X. For the purposes of this invention, the groups X and Y are chosen such that between these groups X. and Y or via these groups X and Y a coupling between polymer A and filler particles B can be produced. The coupling is initiated during or after the coating by the action of electromagnetic radiation, particle radiation and / or thermal energy. The coupling involves at least one group X and at least one group Y. With the coupling of at least one group X and at least one group Y, in the sense of this invention, in particular

a chemical reaction in which the at least one group X reacts with the at least one group Y and leads to the formation of a covalent bond,

the formation of hydrogen bonds between the at least one group X and the at least one group Y and / or

the formation of a coordinative bond, for example by complex formation, in which the at least one group X and the at least one group Y are involved, so that at least one donor / acceptor bond is formed,

Understood.

The coupling can be between the groups X and Y directly or through mediation by one or more other substances, such as. As coupling reagents or crosslinking agents, take place. For the position and number of groups X and Y in the polymers A and filler particles B which can be used according to the invention, the definitions made for the polymers A and the filler particles B apply.

If the coupling according to the invention of the at least one polymer type A with the at least one filler particle type B via the groups Y and X is to take place as a chemical reaction, then the groups X and Y involved are defined in particular according to the following statements.

The PSAs according to the invention contain at least one constituent which contains at least one kind of segments according to the invention which have the general structure (R ⁰ R ⁰⁰ R ⁰⁰⁰ C) -X. R °, R °° and R °°° can be independent of each other saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals, which may also be linked to one another, be the same or different types. It is also possible for the purposes of this invention that the carbon atom listed in (R ⁰ R ⁰⁰ R ⁰⁰⁰ C) -X is itself unsaturated. In this case this carbon atom is linked only to X and one or two of R o, R oo ^oo or R °. The radicals R °, R °° and R °°° may independently contain any number of heteroatoms. The radicals R o, R oo, and R ^oo ° can be low-molecular or polymeric in nature. Up to two of the radicals R °, R °° and R ° ^o ° can also be hydrogen atoms. At least one of R o, R oo and R ^oo ° is linked by a chemical or ionic bonding, physisorption or chemisorption, to a filler of type B. The group necessary for the coupling reaction is designated X.

The at least one segment according to the invention of the structure (R ⁰ R ⁰⁰ R ⁰⁰⁰ C) -X can be reacted with at least one segment which is present in at least one further constituent of the PSA according to the invention and which has the general structure (R * R ** R *** C) -Y, are reacted. R *, R ** and R *** may independently or independently of one another be saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals which may also be linked to one another, identical or different. It is also possible for the purposes of this invention that the carbon atom listed in (R * R ** R *** C) -Y is itself unsaturated. In this case, this carbon atom is linked only to Y and one or two of R *, R ** or R ***. The radicals R *, R ** and R *** may independently contain any number of heteroatoms. The radicals R *, R ** and R *** may be of low molecular or polymeric nature. Up to two of the radicals R *, R ** and R *** can also be hydrogen atoms. At least one of the radicals R *, R ** and R *** is linked by a chemical bond to a type A polymer chain. The group necessary for the coupling reaction is designated Y. In specific embodiments of this invention, one or more of R *, R **, R *** may be of the same kind as R °, R °° or R ° ^o °. Likewise it is according to invention, if the group X and the group Y are of the same kind. In this particular case, the coupling is advantageously carried out by means of a coupling reagent or by the action of a catalyst or initiator. It is particularly advantageous for the purposes of this invention if the coupling reaction is initiated by the action of electromagnetic radiation and / or particle radiation.

For the purposes of this invention, any number of further groups can be used which can react with a group X and / or a group Y. A coupling reaction can occur by chemical reaction directly between the groups X and

Y to form a species (R ° R ^OO R ^OOO C) -X'-Y '- (CR * R ** R ***) is formed (see Fig. 2). X 'and Y' are in the case of a chemical reaction, the reaction products of the groups X and Y. In special cases, a coupling reagent X ^ Y ⁸ or X ^ R ^ Y ^{8 is} required for the coupling of the groups X and Y. X ^a and Y ⁸ are groups capable of reacting with groups X and Y, respectively, and may be the same or different. Furthermore, it is also possible to have two groups X via a coupling reagent YR ^b -

Y and two groups Y via a coupling reagent XR ^b -X. R ^a and R ^b may be saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals and include any number of heteroatoms. The radicals R ^a and R ^b may be of low molecular or polymeric nature.

Table 1 lists some examples of X and Y which can be used according to the invention. Advantageously usable combinations of groups are marked with a cross. Under certain circumstances additional reagents and / or special conditions may be required for the reaction between the groups indicated. Such reagents are then added to the PSA formulation (see section "Further ingredients"). Special conditions such as temperature or radiation are also within the scope of this invention. The table does not claim to be exhaustive, but is merely intended to provide examples of useful groups and combinations of useful groups within the meaning of this invention. Other groups and combinations for corresponding reactions known to the person skilled in the art can likewise be used according to the invention. The radicals contained in Table 1, R ^1, R ^2, R ^3, R ^4, R ^5, R ^6, and R ^a, R ^b, R ^c, R ^d, R ^Θ, R ^f may each independently be saturated or unsaturated, aliphatic or be aromatic hydrocarbon radicals containing any number of heteroatoms and may be of low molecular weight or polymeric nature and / or optionally hydrogen atoms. The radicals may be the same or different in structure as defined above. The radicals R ¹ , R ² and R ³ may be linked to one another, the radicals R ⁵ and R ⁶ may be linked to one another, the radicals R ^a , R ^b and R ^c may be linked to one another and the radicals R ^Θ and R ^f be linked together. Cyclic acid anhydrides such as maleic anhydride or succinic anhydride can be added as a chemical group to polymers A or filler particles B in any desired manner. Maleic anhydride also offers the possibility of being incorporated as comonomer in polymer A.

By the entry "-PI" in Table 1 is meant a group having a photoinitiator function. By irradiation with UV light of suitable wavelength activates the group and, depending on the nature of the photoinitiator, initiates a free-radical reaction or a cationic reaction. Suitable representatives of such groups are type I photoinitiators, that is to say so-called α-splitters such as benzoin and acetophenone derivatives, benzil ketals or acylphosphine oxides, type II photoinitiators, that is to say so-called hydrogen abstractors such as benzophenone derivatives and some quinones, diketones and thioxanthones, and cationic photoinitiators such as "photoacid generators" such as arylated sulphonium or iodonium salts and dimerized arylated imidazole derivatives. Furthermore, triazine derivatives can be used to initiate radical and cationic reactions.

For the purposes of this invention, photoinitiating groups X and / or Y of type I preferably include benzoin, benzoin ethers, for example benzoin methyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl ether, methylolbenzoin derivatives, such as methylolbenzoin propyl ether, 4-benzoyl-1,3 dioxolane and its derivatives, benzil ketal derivatives such as 2,2-dimethoxy-2-phenylacetophenone or 2-benzoyl-2-phenyl-1,3-dioxolane, α, α-dialkoxyacetophenones such as α, α-dimethoxyacetophenone and α, α- Diethoxyacetophenone, α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone and 2-hydroxy-2-methyl-1- (4-iso-propylphenyl) -propanone, 4- (2-

Hydroxyethoxy) -phenyl-2-hydroxy-2-methyl-2-propanone and its derivatives, α-aminoalkylphenones such as 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropan-2-one and 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and ethyl 2,4,6-trimethylbenzoylphenylphosphinate and O-acyl-α-oximinoketone.

According to the invention preferably usable photoinitiating groups of the type Il for example based on benzophenone and its derivatives such as 2,4,6-trimethylbenzophenone or 4,4 ^1-bis (dimethylamino) benzophenone, thioxanthone and its derivatives such as 2-iso- Propylthioxanthon and 2, 4-diethylthioxanthone, xanthone and its derivatives and anthraquinone and its derivatives.

Type II photoinitiators are used particularly advantageously in combination with nitrogen-containing coinitiators, the so-called amine synergists. For the purposes of this invention, preference is given to using tertiary amines. Furthermore, hydrogen atom donors are advantageously used in combination with type II photoinitiators. Examples include substrates containing amino groups. Examples of amine synergists are methyldiethanolamine, triethanolamine, ethyl 4- (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, iso-acrylic 4- (dimethylamino) benzoate, 2- (dimethylaminophenyl ) - Ethanon and unsaturated and thus copolymerizable tertiary amines, (meth) acrylated amines, unsaturated amine-modified oligomers and polymers based on polyester or polyether and amine-modified (meth) acrylates. It is within the meaning of this invention possible if such chemical assemblies are linked to polymers and / or fillers.

For the purposes of these inventions, it is also possible to use any desired combinations of different types of type I and / or type II photoinitiating groups.

In a particularly preferred variant of this invention, groups having a photoinitiating character are contained as groups Y in at least one kind of polymer A.

In a further particularly preferred variant of this invention, groups having a photoinitiating character are contained as groups X in at least one kind of functionalized filler particles B.

If the inventive coupling of the at least one type of polymer A with the at least one type of filler particle B via the groups Y and X via the formation of hydrogen bonds, then the participating groups X and Y are defined according to the following statements. See, for example, D. Philp, J.F. Stoddard, Angew. Chem., 1996, 108, 1242-1286 or C. Schmuck, W. Wienand, Angew. Chem., 2001, 113, 4493-4499.

The PSAs of the invention in this case contain at least one constituent which contains a variety of segments ^having the general structure (R ^# R ^## R ^### C) -X ^# . R ^# , R ^ and R ^ can be independently of one another saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals, which can also be linked to one another, of the same or different type. It is also possible for the purposes of this invention that the carbon atom listed in (R ^# R ^## R ^### C) -X ^{# is} itself unsaturated. In this case, this carbon atom is linked only to X ^# and one or two of R ^# , R ^ or R ^. The radicals R ^# , R ^ and R ^ may independently contain any number of heteroatoms. The radicals R ^# , R ^ and R ^ may be of low molecular or polymeric nature. Up to two of the radicals R ^# , R ^ and R ^ can also be hydrogen atoms. At least one of R ^# , R ^ and R ^ is selected by a chemical or ionic, by chemisorption or physisorption with a Filler particle B linked. The group necessary for the coupling reaction is designated X ^# .

The at least one segment of the structure of the invention (R ^# R ^## R ^### C) -X ^# is capable of hydrogen bonding with at least one functional segment contained in at least one further constituent and having the general structure (R ~ R ~~ RC) -Y ~. R ~, R ^" and R independently of one another may be saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals, which may also be linked to one another, of the same or different types It is also possible within the meaning of this invention for the radical disclosed in (R ~ R ~~ In this case, this carbon atom is linked only to Y ~ and one or two of R ~, R ^" or R. The R ~, R ^" and R radicals may independently contain any number of heteroatoms. The R ~, R ^" and R radicals may be of low molecular or polymeric nature. Up to two of R ~, R ^" and R may furthermore also be hydrogen atoms, and at least one of R ~, R ^" and R is linked to a type A polymer chain by a chemical bond. The group necessary for the coupling reaction is designated Y ~. In specific embodiments of this invention, one or more of R ~, R ^" , R may be of the same kind as R ^# , R ^ or R ™, and it is also according to the invention if the group X ^# and the group Y ~ are of the same kind. In this special case, the coupling takes place by means of a coupling reagent.

For the purposes of this invention, any number of further groups can be used which can form a compound with at least one group X and / or at least one group Y.

A coupling ^reaction can proceed through formation of hydrogen bonds directly between the groups X ^# and Y ~ to form a species (R ^# R ^## R ^### C) -X ^# -Y ~ - (CR ~ R ~~ R) (see Fig. 2). In special cases, the coupling of the groups X ^# and Y ~ ^requires a coupling reagent χ ^#a -Y ~ ^a or X ^#a -R ^a -Y ~ ^a . X ^#a and Y ~ ^a are groups capable of forming hydrogen bonds with Y ~ and X ^# , respectively, and may be the same or different. Furthermore, it is also possible to link two groups X ^# via a coupling reagent Y ~ -R ^b -Y ~ and two groups Y ~ via a coupling reagent X ~ -R ^b -X ~. R ^a and R ^b may be saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals and include any number of heteroatoms. The radicals R ^a and R ^b may be of low molecular or polymeric nature. The coupling groups may be monodentate or preferably polydentate. Teeth refers to the ability of a group to form a specific number of hydrogen bonds. Hydrogen bonds between monodentate or preferably multidentate functional segments are known as structuring elements from various examples. In nature, hydrogen bonds between complementary functional segments serve to build up deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). A special combination of donor and acceptor sites makes it possible that couplings can only be made according to the key-lock principle. If, for example, the functional segments α (type "key") and β (type "lock") are complementary segments that can form hydrogen bonds, then a connection between α and β is possible, between α and α as well as β and β However not. Nature is restricted to the two organic base pairs AdeninfThymine (instead of thymine uracil in RNA) as bidentate segments and cytosine / guanine as tridentate segments when selecting the functional segments.

For the purposes of this invention, polymers A and filler particles B with groups based on adenine, thymine, uracil, cytosine, guanine, their derivatives and other compounds which are capable of forming hydrogen bonds according to the key-lock principle, such as 2-ureido-4-pyrimidone and its derivatives, 2,6-diacetylaminopyridine and its derivatives, diacetylpyrimidine and its derivatives, and ureidoacylpyrimidine and its derivatives. This list does not claim to be exhaustive. On the contrary, other systems are known to the person skilled in the art which can be used according to the invention. If one chooses this type of functionalization, then wearing in the sense of this invention, either the at least one type of polymer A groups of the type "key" and the at least one Füllstoffpartikortsorte B groups of the type "lock" or vice versa. Figure 3 shows two examples of the coupling of reactive species through hydrogen bond formation through the use of two complementary groups, the direct coupling of polymer A and filler particles B, and the coupling of polymer A and filler particle B using a coupling reagent.

According to the invention also the coupling of groups via coordinative bonds is possible. Examples of coordinative bonds are ligand-central atom bonds in complexes, ie the formation of a coordinative bond with metal atoms, which may be elemental, in the form of metal salts and / or in the form of metal complexes, as well as all other donor-acceptor bonds (see for example, D. Philp, JF Stoddard, Angew. Chem., 1996, 108, 1242-1286; M. Rehahn, Acta Polym., 1998, 49, 201-224 or BGG Lohmeijer, US Schubert, J. Polym. Be. A polym. Chem., 2003, 41, 1413-1427),

If one chooses this coupling principle in the context of this invention, then the PSA contains filler particles of the type B, the groups with the general structure (R ^§ R ^§§ R ^§§§ C) -X ^§ contain. R ^§ , R ^§§ and R ^§§§ can be independently of one another saturated or unsaturated, aliphatic or aromatic hydrocarbon ^radicals , which may also be linked to one another, of identical or different nature. It is also possible for the purposes of this invention that the carbon atom listed in (R ^§ R ^§§ R ^§§§ C) -X ^{§ is} itself unsaturated. In this case, this carbon atom is linked only to X ^§ and one or two of R ^§ , R ^§§ or R ^§§§ . The radicals R ^§ , R ^§§ and R ^§§§ can independently contain any number of heteroatoms. The radicals R ^§ , R ^§§ and R ^§§§ may be of low molecular or polymeric nature. Up to two of the radicals R ^§ , R ^§§ and R ^§§§ can also be hydrogen atoms. At least one of R ^§ , R ^§§ and R ^§§§ is linked to a type B filler ^particle by chemical or ionic bonding, chemisorption or physisorption. The group necessary for the coupling reaction is designated X ^§ . Simultaneously, the pressure-sensitive adhesive polymer contains the kind A, the groups having the general structure (R'R ^{^} R ^{^} CJ-Y "contain. R ^=, R ⁼⁼ and R ⁼⁼⁼ may independently be saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals be, which also may be linked to each other, similar or different kind. It is also possible in the sense of this invention that the carbon atom ^* listed in (R'R ^{^} R ^{^} CJ-Y itself is unsaturated. in this case this carbon atom is with Y "and one or two of the radicals R ^=, R or R ⁼⁼ ⁼⁼⁼ linked. the radicals R ^=, R and R ⁼⁼ ⁼⁼⁼ each other can include independently any number of heteroatoms. the radicals R ^=, R ⁼⁼ and R ⁼⁼⁼ may be of low molecular or polymeric nature and up to two of R ⁼ , R ⁼⁼ and R ⁼⁼⁼ may also be hydrogen atoms, at least one of R ⁼ , R ⁼⁼ and R ^{= ==} is by a chemical bond with a polymer chain d he linked variety A The time required for the coupling reaction is "hereinafter. The groups X and Y ^§" with Y may be the same or different type. If they are different, then one of the group types takes on the donor function and the other the acceptor function required for the formation of coordinative bonds. If both groups are of the same type, the formation of the coordinative bond via a coupling reagent takes place.

The groups in the polymers A and the filler particles B are advantageously designed to be capable of forming coordinative bonds with type M metals which may be elemental, in the form of metal salts or in the form of metal complexes can. Metal complexes can also be multinuclear. Monodentate or multidentate segments may be used. The coupling principle is shown schematically in Figure 4. At least two groups of the type "key" couple by coordinating M, which takes over the function "lock". In the formation of coordinate bonding, the structure may change from M to M '. This can be expressed in altered oxidation states but also in an altered ligand structure and / or composition. When using metal atoms, it is particularly advantageous for the purposes of this invention to take special precautions for the dispersion of M in the PSA. This is preferably done by selecting particularly suitable counterions, if they are metal salts, or particularly suitable complexing ligands, if they are metal complexes. Suitable counterions and complex ligands therefore assume the function of compatibilizers and dispersants. It is particularly advantageous to disperse the metal atom M in a fusible matrix which does not contain any constituents capable of coordinating with M. This mixture is metered in just before the coating of the remaining PSA formulation which contains at least one type of polymer A and at least one type of filler particle B.

Particularly preferred is coupling using chelating segments. Examples of ligands which can be used as groups are bipyridine and terpyridine and their derivatives, acetylacetonate and its derivatives, ethylenediaminetetraacetic acid and its derivatives, nitrilotriacetic acid and its derivatives, hydroxyethylethylenediaminetriacetic acid and its derivatives,

Diethylenetriaminepentaacetic acid and its derivatives and carboxylic acids. This list does not claim to be exhaustive. On the contrary, other systems are known to the person skilled in the art which can be used according to the invention. These groups are not reactive with each other. All components containing these groups can therefore be used in a mass flow. The coupling of the groups takes place as soon as the metal atom M-containing mixture is added to the mass flow, which happens in the context of this invention immediately before the coating.

Suitable metal atoms in the context of this invention are all those chemical elements which are capable of acting as acceptors for coordinative bonds. These are alkaline earth metals, preferably Ca and / or Mg, transition metals, preferably Ti, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, W, Re, Os, Ir and / or Pt and Al and lanthanides. Suitable compatibilizers and dispersing agents for these metal atoms which can be used according to the invention are, for example, aliphatic or aromatic, saturated or alcoholic alkoxides unsaturated, any number of heteroatom-containing molecules, which may be of low molecular weight or polymeric nature. Also useful are open chain or cyclic unsaturated hydrocarbons containing any number of heteroatoms and which may be of low molecular weight or polymeric nature. Further dispersing aids which can be used according to the invention and compatibilizers for M are low-molecular chelating compounds of organic type.

In general, M can be an acceptor group ("key") which can form a coordinative bond in conjunction with a lock-type donor group. The acceptor group may in this case be bound to polymer A and filler particles B or also be used as coupling reagents. This general case is shown schematically in Figure 5. It is further in accordance with the invention to use acceptor group-equipped polymers A and filler particles B in combination with donor group-bearing coupling reagents.

For the purposes of this invention, any combination of different types of coupling reactions may be used. According to the invention, at least one type of coupling reaction is used.

Process for the production of self-adhesive products

The preparation of self-adhesive products according to the invention comprises the process steps of formulation / compounding, coating and crosslinking.

compounding

The formulations of the invention may be prepared using solvents in solvent kneaders or z. B. also be prepared by the use of high-speed disperse. Preferably, however, such formulations are prepared solvent-free. For this purpose kneaders are available in discontinuous operation and in continuous operation extruders, such as twin-screw extruders. Suitable compounding units in the context of this invention are those which contain dispersive and optionally distributive mixing elements. Dispersive mixing elements ensure the finest possible distribution of the filler particles in the formulation, while the distributive elements homogenize molten constituents such as resins or polymers in a mixture of the PSA formulation. In solvent-free discontinuous In particular, Banbury mixers, Buss kneaders or Baker-Perkins Ko-kneaders can be used. In continuous operation, twin-screw extruders in co-rotating mode can be used with preference.

coating process

For the purposes of this invention, the coating method can be a doctor blade method, a doctor blade method, a roller bar nozzle method, an extrusion die method, a casting nozzle method and a foundry method. Also according to the invention are application methods such as roller application method, printing method, screen printing method, anilox roller method, inkjet method and spray method. To feed the coating unit according to the invention can optionally be a metering and mixing unit and coating unit a conveying and / or mixing unit, for. As a single-screw or twin-screw extruder, be interposed. The optional extruder can be heated separately.

crosslinking process

Particularly preferred is the initiation of crosslinking of the PSA after its coating. For this purpose, a radiation chemical process is particularly advantageous.

As a very preferred variant, which can be used in the context of this invention, the crosslinking is called ultraviolet radiation. By means of brief action of

Light in a wavelength range between 200 to 400 nm becomes the coated one

Material which in this embodiment of the invention, the photoinitiator functions preferably contains as groups X and / or groups Y, irradiated and cross-linked. For this purpose, mercury high-pressure or medium-pressure lamps are used in particular at a power of 80 to 240 W / cm. Further radiation sources which can be used in the context of this invention are the radiation sources known to the person skilled in the art. Optionally, that will

Emission spectrum of the lamp matched to the photoinitiator used or the type of photoinitiator adapted to the lamp spectrum. The irradiation intensity is adapted to the respective quantum yield of the UV photoinitiator, the degree of crosslinking to be set and the web speed.

Furthermore, it is preferably possible to crosslink the PSA formulations according to the invention after their coating with electron beams. This can also be done in

Combination with UV crosslinking done. Typical irradiation devices that can be used are linear cathode systems, scanner systems or Segment cathode systems, as far as it is electron beam accelerator. Typical acceleration voltages are in the range between 50 kV and 1 MV, preferably 80 kV and 300 kV. The applied radiation doses are between 5 and 250 kGy, in particular between 20 and 100 kGy.

For the purposes of this invention, it is furthermore preferably possible to realize the crosslinking by the action of thermal energy. This may optionally be done in combination with one or more radiation-chemical methods. If thermal energy is used to initiate the crosslinking reaction, then it must be ensured that the crosslinking process has not yet progressed too far during the coating since this alters the coating behavior of the formulation. In this case, it is particularly preferred to prepare a compound which already contains filler particles of grade B and polymers of grade A, but groups X and Y are selected so that they can not react directly with one another but only through the intermediation of a crosslinker or a coupling reagent. Crosslinkers or coupling reagents are then preferably metered into the otherwise fully homogenized compound immediately before coating and mixed with it. Particularly preferred is a two- or multi-component process is performed, in which all raw materials are divided into at least two mass stocks that a spatial separation is guaranteed until just before the coating of all those raw materials that are capable of a thermal reaction with each other. The thermal energy is then either taken from the preheated mass flows, made available by adjusting a temperature of the coating unit or realized via a heat channel or an infrared path after the coating. It is also possible according to the invention to utilize the thermal energy released in one or more exothermic reactions for the course of this thermal reaction. Combinations of these process possibilities, in particular with the radiation-chemical crosslinking processes, are possible in the context of this invention.

Very preferred for the purposes of this invention, the production of self-adhesive products according to the invention takes place in a continuous process in which the process steps of compounding, coating and crosslinking are coupled directly and thus an in-line process is used. Self-adhesive products

product constructions

The pressure-sensitive adhesives prepared by the processes according to the invention can be used for the construction of various self-adhesive products such as, for example, self-adhesive tapes or self-adhesive films. Inventive structures of self-adhesive products are shown in FIG. Each layer in the self-adhesive tape assemblies of the invention may optionally be foamed.

In the simplest case, a self-adhesive product according to the invention consists of the pressure-sensitive adhesive in a single-layered structure (structure in FIG. 6.1). This structure can optionally one-sided or both sides with a release liner, z. B. a release film or a release paper are covered. The layer thickness of the PSA is typically between 1 .mu.m and 2000 .mu.m, preferably between 5 .mu.m and 1000 .mu.m.

The PSA may also be on a support, in particular a film or paper support or a textile fabric (structure in Figure 6.2). The support may be pretreated on the side facing the PSA side in accordance with the prior art, so that, for example, an improvement in the pressure-sensitive adhesive anchorage is achieved. Likewise, the page can be equipped with a functional layer, which can act as a barrier layer, for example. The backing may be pretreated according to the prior art, so that, for example, a release effect is achieved. The carrier back can also be printed. The PSA may optionally be covered with a release paper or release liner. The PSA has a typical layer thickness between 1 .mu.m and 2000 .mu.m, preferably between 5 .mu.m and 1000 .mu.m.

The construction according to FIG. 6.3 is a double-sided self-adhesive product which is used as a middle layer z. B. a carrier film, a backing paper, a textile

Contains sheet or a foam carrier. Adhesive adhesives of the same or different types and / or identical or different layer thicknesses according to the invention are used in this construction as upper and lower layers. The carrier may be pretreated on one or both sides according to the prior art, so that, for example, an improvement of the pressure-sensitive adhesive anchoring is achieved.

Likewise, one or both sides may be provided with a functional layer which may act as a barrier layer, for example. The pressure-sensitive adhesive layers can optionally covered with release papers or release liners. The pressure-sensitive adhesive layers typically have layer thicknesses of between 1 μm and 2 000 μm, preferably between 5 μm and 1000 μm, independently of one another.

As a further double-sided self-adhesive product, the structure according to FIG. 6.4 is a variant according to the invention. A pressure-sensitive adhesive layer according to the invention carries on one side a further PSA layer which, however, can be of any desired nature and therefore need not be in accordance with the invention. The structure of this self-adhesive product can optionally be covered with one or two release films or release papers. The pressure-sensitive adhesive layers, independently of one another, have layer thicknesses of typically between 1 μm and 2000 μm, preferably between 5 μm and 1000 μm.

As in the construction in FIG. 6.4, the structure according to FIG. 6.5 is also a double-sided self-adhesive product which contains a pressure-sensitive adhesive composition according to the invention and any desired further. However, the two pressure-sensitive adhesive layers in FIG. 6.5 are separated from one another by a carrier, a carrier film, a carrier paper, a textile fabric or a carrier foam. The carrier may be pretreated on one or both sides according to the prior art, so that, for example, an improvement of the pressure-sensitive adhesive anchoring is achieved. Likewise, one or both sides may be provided with a functional layer which may act as a barrier layer, for example. The pressure-sensitive adhesive layers can optionally be covered with release papers or release liners. The pressure-sensitive adhesive layers, independently of one another, have layer thicknesses of typically between 1 μm and 2000 μm, preferably between 5 μm and 1000 μm.

The self-adhesive product according to the invention according to FIG. 6.6 contains a layer of material according to the invention as a middle layer, which is provided on both sides with any desired or different types of pressure-sensitive adhesive. One or both sides of the middle layer may be provided with a functional layer which may act as a barrier layer, for example. In the case of the outer pressure-sensitive adhesive layers, it is not necessary to use PSAs according to the invention. The outer pressure-sensitive adhesive layers can optionally be covered with release papers or release liners. The outer pressure-sensitive adhesive layers, independently of one another, have layer thicknesses of typically between 1 μm and 2000 μm, preferably between 5 μm and 1000 μm. The thickness of the middle layer is typically between 1 .mu.m and 2000 .mu.m, preferably between 5 .mu.m and 1000 .mu.m. Test Methods

Numerical values for systems according to the invention are listed in the description of this invention and reference is made to test methods by means of which such data can be determined. These test methods are summarized below.

Determination of processing properties (Test A)

Melt viscosities (test A1) and first normal stress differences are calculated for solvent-free, unvarnished test samples as a function of the shear rate and temperature using a PC-controlled high-pressure capillary rheometer from Göttfert (model

Rheograph 2002) from the measured pressure losses in the stationary flow range. For example, a flat slot with the geometry 23 mm × 25 mm × 0.16 mm (L × W × H) is used as the capillary. As values for the shear rates, viscosities and first normal voltage differences, corrected data are given in this specification.

The shear rate for the tests is 1000 s ^{~ 1} . The measuring temperature depends on the

Type of material investigated and is given together with the measurement results. From the data on the shear rate, viscosity and first normal stress difference, the R value is determined as the ratio of the first normal stress difference and the product of viscosity and shear rate (Test A2).

Determination of Gel Content (Test B)

Coated and crosslinked solvent-free PSA samples are sealed in a polyethylene nonwoven bag. Soluble components are extracted with toluene over a period of three days with daily solvent exchange. From the difference in sample weights before extraction and after extraction, the gel value is determined as a percentage of the weight fraction of the polymer that is not extractable with toluene.

Determination of the bond strength (test C)

The peel strength (bond strength) is tested on the basis of PSTC-1. On a 25 micron thick PET film, a 50 micron thick pressure-sensitive adhesive layer is applied. A 2 cm wide strip of this pattern is duplicated on a ground steel plate by five times

Overrolling glued by means of a 5 kg roll. The plate is clamped and the Self-adhesive strip on its free end on a tensile tester peeled at a peel angle of 180 ° at a speed of 300 mm / min.

Determination of shearing life (test D)

The test is based on PSTC-7. On a 25 micron thick PET film, a 50 micron thick pressure-sensitive adhesive layer is applied. A 1, 3 cm wide strip of this pattern is glued on a polished steel plate over a length of 2 cm with a 2 kg roll by twice double rolling over. The slides are equilibrated for 30 min under test conditions (temperature and humidity) but without load. Then the test weight is added so that a shear stress is generated parallel to the bond area and the time is measured until the bond fails.

Table 1

Claims

claims

A process for the preparation of a pressure-sensitive adhesive based on at least one polymer, in which a crosslinking of the at least one polymer is carried out, wherein the polymer has functional groups Y, wherein the polymer is additionally mixed with at least one kind of functionalized particles which comprise at least one non-polymeric base unit characterized in that the particles have a surface modification of the base unit, wherein the surface modification of the particles has at least one sort of functional groups X, and wherein the crosslinking of the polymer is based at least in part by a reaction of the functional groups X of the particles and the functional groups Y of the polymer is effected.

2. The method according to claim 1, characterized in that the at least one base unit of the at least one functionalized particle type is an amorphous or crystalline oxide of inorganic nature, in particular a metal oxide or a half metal oxide.

3. The method according to claim 1, characterized in that the at least one base unit of the at least one functionalized particle type is an alkaline earth salt.

4. The method according to claim 1, characterized in that the at least one base unit of the at least one functionalized particle type a

Silicate-based mineral, in particular a clay mineral.

5. The method according to at least one of the preceding claims, characterized in that the functional groups Y of the at least one polymer and / or the functional

Groups X of at least one particle type at least partially photoinitising character.

6. The method according to at least one of the preceding claims, characterized in that the surface modification of the at least one functionalized particle type by organosilanes, surfactants, organotitanium compounds, fatty acids and / or polyelectrolytes is effected.

7. The method according to at least one of the preceding claims, characterized in that the reaction for effecting the crosslinking of the PSA is a coupling reaction, in particular one to form covalent bonds to form hydrogen bonds and / or to form coordinative bonds.

8. The method according to at least one of the preceding claims, characterized in that the crosslinking reaction is initiated essentially by radiation chemistry, in particular by the action of UV radiation.

9. The method according to at least one of the preceding claims, characterized in that the at least one functionalized particle type in the form of singular spherical particles, singular platelet-shaped particles and / or singular rod-shaped particles is present.

10. The method according to at least one of the preceding claims, characterized in that the at least one functionalized particle type is present in the form of particle aggregates formed from a plurality of primary particles.

11. The method according to claim 9 or 10, characterized in that the particles or the particle aggregates a spatial extent of not more than 1000 nm, preferably in at least one spatial direction of not more than 250 nm, very preferably in at least one spatial direction of not more than 100 nm.

12. The method according to at least one of the preceding claims, characterized in that the weight fraction of functionalized particles in the pressure-sensitive adhesive is up to 50%, preferably up to 20%, very preferably up to 12%.

13. A pressure-sensitive adhesive based on at least one crosslinked polymer component, in which the crosslinking of the polymer component is effected at least in part by incorporation of functionalized particles, the particles having at least one non-polymeric base unit and a surface modification of this base unit, wherein the surface modification of the particles is at least one grade functional groups X which are capable of reacting with functional groups Y present in the polymer component.

14. Pressure-sensitive adhesive according to claim 13, obtainable by a process according to one of claims 1 to 12.

15. Use of surface-modified functionalized particles with a non-polymer base unit as crosslinking reagents for crosslinking polymers for the preparation of PSAs.

16. Self-adhesive products, provided with a pressure-sensitive adhesive according to one of claims 13 or 14.